JP5480909B2 - Cerium phosphate and / or terbium phosphate, optionally with lanthanum, phosphor resulting from said phosphate, and method of making the phosphor - Google Patents

Description

  The present invention relates to cerium phosphate and / or terbium phosphate, optionally with lanthanum, a phosphor resulting from the phosphate, and a method of making the phosphor.

  Lanthanum, terbium and cerium mixed phosphates, and lanthanum and terbium mixed phosphates (hereinafter generally referred to as LAP) are well known for their luminescent properties. For example, when these LAPs contain cerium and terbium, they emit bright green light when irradiated with certain high-energy radiation (ultraviolet or VUV radiation for illumination or display systems) having a wavelength below that of the visible region To do. Phosphors that make use of this property are widely used on an industrial scale, for example, in three-color fluorescent lamps, in backlight systems for liquid crystal displays, or in plasma systems.

  Several methods are known for making LAPs. There are two types of these methods. First, there is a “dry” method in which a phosphating of a mixture of oxides or mixed oxides is carried out in the presence of diammonium phosphate. These methods, which can be relatively long and complex, particularly cause problems in controlling the size and chemical uniformity of the resulting product. Another method is called “wet method” and is summarized. In these methods, the synthesis of rare earth metal mixed phosphates or mixtures of rare earth metal phosphates is carried out in a liquid medium.

  These various syntheses result in mixed phosphates that require heat treatment at a high temperature of about 1100 ° C. in a reducing atmosphere, generally in the presence of a fluxing agent or flux. This is because terbium and, if necessary, cerium, need to be in the trivalent oxidation state in order to be the most effective phosphor that can be a mixed phosphate.

  The above dry and wet methods result in uncontrolled, particularly insufficiently narrow particle size phosphors that are even more prominent due to the need for high temperature thermal activation in a reducing atmosphere using flux. There is a drawback. This disadvantage generally results in further disturbances in the particle size, thus resulting in phosphor particles having a non-uniform particle size. These phosphor particles may additionally contain large or small amounts of impurities associated with the use of the flux and ultimately exhibit poor luminous performance.

  A method is proposed in patent application EP 0 582 621, which makes it possible to improve the particle size of LAP by means of a narrow particle size distribution, but this method results in a particularly high performance phosphor. In the process described, nitrates are used in particular as rare earth metal salts, and their use as a base for aqueous ammonia with the disadvantage of nitrogen product release is recommended. Thus, although this method actually results in a high-performance product, the implementation becomes more complicated if the increasingly restrictive environmental protection laws that prohibit or limit such releases are to be followed. There is.

  Although it is certainly possible to use particularly strong bases other than aqueous ammonia, such as alkali metal hydroxides, the latter leads to the presence of alkalis in the LAP, which in turn contributes to the emission properties of the phosphor. When using these, it is considered that the mercury vapor lamp may deteriorate.

  Therefore, there is a production method that does not give negative results with respect to the luminescent properties of the resulting product, uses little or no nitrate or aqueous ammonia, and does not require the use of flux in the production of phosphors. Currently needed.

European Patent Application No. 0586211

  It is an object of the present invention to improve the method of making LAPs that limit the release of nitrogen products and even do not release these products.

  Another object of the present invention is to provide a phosphor that still has the same or better properties than those currently known.

  Thus, according to a first aspect, the present invention provides a rare earth metal (Ln) phosphate. Ln represents at least one rare earth metal selected from cerium and terbium, or lanthanum in combination with at least one of the two rare earth metals. This rare earth metal (Ln) phosphate has a rhabdophane type or rhabdophene / monazite mixed type crystal structure and is characterized by containing lithium and having a maximum lithium content of 300 ppm.

  The invention also relates to rare earth metal (Ln) phosphates, where Ln has the same meaning as above. This rare earth metal (Ln) phosphate has a monazite-type crystal structure, contains lithium, and has a maximum lithium content of 300 ppm.

  According to another aspect, the present invention also relates to a phosphor based on rare earth metal (Ln) phosphate, wherein Ln has the same meaning as above. This phosphor has a monazite-type crystal structure, contains lithium, and has a lithium content of up to 75 ppm.

  The phosphor of the present invention has excellent emission characteristics and excellent lifetime despite the presence of lithium, an alkali metal. These phosphors can even show emission yields that are superior to known products.

  Other features, details and advantages of the present invention will become more apparent upon reading the following description and various specific but non-limiting examples for the purpose of illustrating the present invention. Let's go.

  In the rest of the description, unless otherwise specified, all ranges or boundaries of a value mentioned include the value of the boundary, and thus the value range or boundary defined in this way is at least above the lower limit and / or maximum. Include any value that is less than or equal to the upper limit.

  Note that minimum and maximum values are mentioned with respect to the lithium content described in the remaining description of phosphates and phosphors. It is to be understood that the present invention includes any range of lithium content defined by any one of these minimum values and any one of these maximum values.

  The term “rare earth metal” means, in the rest of the description, an element of the group consisting of yttrium and elements of the periodic table including atomic numbers 57 to 71.

  The lithium content is also measured here by two techniques and is specified here and throughout the description. The first technique is a fluorescent X-ray technique, which makes it possible to measure a lithium content that is at least about 100 ppm. This technique will be used especially for phosphates or precursors or phosphors with the highest lithium content. The second technique is ICP (inductively coupled plasma) -AES (atomic emission spectroscopy) or ICP-OES (emission spectroscopy) technique. This technique will be used here, particularly for precursors or phosphors with the lowest lithium content, especially for contents below about 100 ppm.

  As described above, the present invention relates to two types of products, hereinafter referred to as precursors, and phosphors obtained from these phosphates. The phosphor itself has sufficient emission properties to allow direct use in the desired application. The precursors do not have luminescent properties, or in some cases have luminescent properties that are too weak for use in these same applications.

  Here, these two types of products will be described more precisely.

Phosphate or Precursor The phosphate of the present invention is provided according to two embodiments that differ from each other because of their crystallographic structure. First, features common to these two embodiments will be described.

The phosphate of the present invention is basically in the orthophosphate form of the formula LnPO ₄ , preferably in the form of LnPO ₄ , although in practice the presence of entities containing other residual phosphates is possible. Is as defined above.

  The phosphate of the present invention is a phosphate of cerium or terbium or a combination of these two rare earth metals. These phosphates may be lanthanum phosphates combined with at least one of these two rare earth metals, and most particularly lanthanum, cerium and terbium phosphates. Good.

  The proportion of each of these various rare earth metals can vary within a wide range, but in particular can vary within the range of values listed below. Therefore, the phosphate of the present invention basically comprises a product that can correspond to the following general formula (1).

_{La x Ce y Tb z PO 4} (1)

  Here, the sum of x + y + z is equal to 1, and at least one of y and z is other than 0.

  In the above formula (1), x may be 0.2 to 0.98, more preferably 0.4 to 0.95.

Due to the presence of other residual phosphate-containing entities described above, the Ln (total rare earth metal) / PO ₄ molar ratio can be less than 1 for the total phosphate.

  In the formula (1), when at least one of x and y is other than 0, z is preferably 0.5 at maximum, but z may be 0.05 to 0.2, particularly 0.1 to 0.2. .

  If both y and z are other than 0, x may be 0.2 to 0.7, especially 0.3 to 0.6.

  If z is equal to 0, y may be 0.02 to 0.5, more particularly 0.05 to 0.25.

  If y is equal to 0, z may be 0.05 to 0.6, more particularly 0.08 to 0.3.

  If x is equal to 0, z may be 0.1 to 0.4.

  By way of example only, a more specific composition can be mentioned.

  The phosphate of the present invention may contain other elements that have traditionally served as accelerators of luminescent properties or stabilizers of the degree of oxidation of cerium and terbium elements. As an example of these elements, mention may be made in particular of boron and other rare earth metals such as scandium, yttrium, lutetium, gadolinium. When lanthanum is present, the rare earth metal can in particular be present as an alternative to this element. These promoter or stabilizer elements are generally present in an amount of up to 1% by weight relative to the total weight of the phosphate of the invention in the case of boron and up to 30% for the other elements mentioned above. To do.

  The phosphates of the present invention are also characterized by the particle size of these phosphates.

  These phosphates are actually composed of particles generally having an average diameter of 1 μm to 15 μm, in particular 2 μm to 6 μm.

  The average diameter mentioned is the volume average of the diameter of the particle population.

  Here, the particle size value mentioned in the remaining description is measured for a sample in which particles are dispersed in water for 1 minute 30 seconds by ultrasonic (130 W) using a Malvern particle size measuring device.

  Furthermore, these particles preferably have a low dispersion index, typically up to 0.5, preferably up to 0.4.

  The “dispersion index” of a particle population means, for the purposes of this description, the ratio I as defined below.

_{I = (φ 84 -φ 16)} / (2 × φ 50)

Here, phi ₈₄ is the diameter of the particles, 84% of the particles have a diameter less than phi _84.

phi ₁₆ is the diameter of the particles, but 16% of the particles have a diameter less than phi _16.

φ ₅₀ is the average diameter of the particles, but 50% of the particles have a diameter less than φ ₅₀ .

  The definition of the dispersion index described here for the precursor particles also applies to the phosphor in the rest of the description.

  An important feature of the phosphate of the present invention common to these two embodiments is the presence of lithium. The amount of lithium depends on the embodiment. Lithium may be assumed to be chemically bonded to one or more constituent chemical elements of the phosphate rather than simply present in the phosphate as a mixture with other components of the phosphate. it can.

  According to one particular embodiment, these phosphates contain only lithium as the alkali metal element.

  The two embodiments of the phosphate of the present invention further have the more specific features described below.

  In a first embodiment of the present invention, the phosphate has a labudophene type or a rubudofen / monazite mixed crystal structure.

  These crystal structures, referred to here and throughout the rest of the description, can be demonstrated by X-ray diffraction (XRD) techniques.

  Thus, the phosphate can have a labudophene-type structure, in which case the phosphate can have a pure phase, ie the XRD diagram shows only one labdophene phase. Nevertheless, the phosphate of the present invention may not be a pure phase, in which case the XRD diagram of the product shows the presence of very little residual phase.

  The phosphate can also have a rhabdofen / monazite mixed structure.

  The rubded phen type or the rubbed phen / monazite mixed type structure corresponds to a phosphate that has not been heat-treated at the end of the preparation or that has been heat-treated at a temperature usually below 600 ° C., in particular 400-500 ° C.

  The lithium content of the phosphate according to the first embodiment is at most 300 ppm, in particular at most 250 ppm, and more particularly at most 100 ppm. This content, both here and throughout the rest of the description, is represented by the mass of elemental lithium relative to the total mass of phosphate.

  A minimum lithium content is not essential. The minimum lithium content can correspond to the minimum value detectable by the analytical technique used to measure the lithium content. However, this minimum lithium content is usually at least 10 ppm, in particular at least 90 ppm.

  The labdofene-type crystal structure phosphate is composed of particles composed of crystallite aggregates, and the size of the crystallites measured in the (012) plane is at least 25 nm, in particular at least 30 ppm. . This size may vary depending on the temperature of the heat treatment or the temperature of calcination applied to the precursor during fabrication.

  Here and throughout the rest of the description, the value measured by XRD is specified to correspond to the size of the coherent domain calculated from the width of the main diffraction line corresponding to the crystal plane (012). For this measurement, the book Theory et technique de la radiocristallogie [Radiocrystallographic theory and technique], A.M. The Scherrer model described in Guinier, Dunod, Paris, 1956 is used.

  This size determination by the XRD technique becomes very difficult in the case of a rubudophene / monazite mixed structure, so the discussion so far regarding crystallite size is basically applicable to the phosphate of the labudofen structure. Please note that.

  This crystallite size, which is larger than the crystallite size of prior art phosphates obtained after heat treatment at the same temperature and can also have the same particle size, reflects better crystallization of the product.

  The phosphate of the first embodiment without heat treatment is generally hydrated, but to remove most of this residual water and to provide a substantially anhydrous rare earth metal phosphate, for example from 60 Simple drying performed at 100 ° C is sufficient. On the other hand, the remaining small amount of water is removed by calcination at higher temperatures above about 400 ° C.

  In a second embodiment, the phosphate has a monazite-type crystal structure, which is more stringent than in the first embodiment, at least 600 ° C., preferably 700 to 1000. Corresponds to the product obtained after heat treatment carried out at a temperature of ° C.

  With respect to the previous embodiment, the phosphate can in this case have a pure phase, ie the XRD diagram shows only one monazite phase. Nevertheless, the phosphate of the present invention may not be a pure phase, in which case the XRD diagram of the product shows the presence of very little residual phase.

  The lithium content of the phosphate according to this second embodiment is a maximum of 300 ppm, in particular a maximum of 250 ppm.

  With respect to the first embodiment, the minimum lithium content is not essential. This minimum lithium content can correspond to the minimum value detectable by the analytical technique used to measure this content. However, this minimum lithium content is usually at least 10 ppm, in particular at least 90 ppm.

  The phosphates of the monazite crystal structure consist of particles composed of crystallites themselves, and the size of the crystallites measured in the (012) plane is at least 70 nm, in particular at least 80 nm. This size again varies with the temperature of the calcination applied to the precursor during fabrication. Here again, the same observations can be made regarding the better crystallization of the phosphate of the present invention compared to prior art phosphates having the same structure.

  The phosphates or precursors according to the invention are generally subjected to calcination or heat treatment at temperatures above 600 ° C., preferably 800 to 900 ° C., at wavelengths that are variable depending on the composition of the product. After exposure to light of a given wavelength (e.g. for lanthanum, cerium and terbium phosphates, after exposure to light of wavelength 254 nm, emission at a wavelength of about 550 nm, i.e. in the green region) In order to obtain a true phosphor that has luminescent properties but can be used directly in the desired application, it is possible to further improve these luminescent properties by post-processing the product, It is even more necessary.

  The boundary between mere rare earth metal phosphates and true phosphors is still arbitrary, but from this value it is believed that the product can be used directly as the user allows. It is understood that it depends only on the threshold.

  In this case, very generally, it is possible to identify and identify rare earth metal phosphates according to the invention that have not been heat-treated above about 900 ° C. as phosphor precursors. This is because such products generally have luminescent properties that can be considered not to meet the minimum luminance requirements of commercial phosphors that can then be used directly without any conversion. Conversely, a rare earth metal phosphate that exhibits an appropriate brightness that is sufficient for direct use by an applicator, for example, in a lamp or television screen after appropriate processing is described as a phosphor. It is possible.

  The phosphor according to the invention is described below.

Phosphors The phosphors of the present invention have shared properties with the phosphates or precursors just described.

  Thus, the phosphor has the same particle size characteristics as the phosphate or precursor, ie an average particle size of 1 to 15 μm with a dispersion index of up to 0.5. Everything that has been described above regarding the particle size of the precursor applies here as well.

  The phosphor is also an orthophosphate type of the same formula as above, and has a composition that is almost identical to that of the precursor. The relative proportions of lanthanum, cerium and terbium mentioned above for the precursors also apply here. Similarly, the phosphor can include the accelerator or stabilizer elements mentioned above for phosphate in the indicated proportions.

  These phosphors have a monazite crystal structure. According to one preferred embodiment, the phosphor of the present invention has a pure phase, ie the XRD diagram shows only one monazite phase. Nevertheless, the phosphor of the present invention may not be a pure phase, in which case the XRD diagram of the product shows the presence of a very small amount of residual phase.

  The phosphor contains lithium in an amount of up to 75 ppm, in particular up to 50 nm. This content is again expressed as the mass of potassium element relative to the total mass of the phosphor.

  A minimum lithium content is not essential. Again, for phosphate, this minimum lithium content can correspond to the minimum detectable by the analytical technique used to measure the content of this element. However, this minimum lithium content may usually be at least 10 ppm.

  According to one particular embodiment, the phosphor does not contain an alkali metal element other than lithium.

  The phosphor of the present invention is composed of particles having a coherent length measured at the (012) plane of at least 250 nm. This coherent length, measured by the same technique as for the precursor, may vary depending on the temperature of the heat treatment or the temperature of the calcination applied to the phosphor during fabrication.

  This coherent length may in particular be at least 350 nm.

  As with the precursor, it is again observed that this coherent length is greater than the coherent length of prior art phosphors obtained after heat treatment at the same temperature and which can also have the same particle size. This observation again reflects a better crystallization of the products, which is beneficial for the emission properties of these products, especially for the luminous efficiency.

  The particles constituting the phosphor of the present invention can have a substantially spherical shape. These particles are dense.

  Here, a method for producing the precursor and phosphor of the present invention will be described.

Method of Making a Phosphate or Precursor The first method described relates to the preparation of a precursor according to the first embodiment, ie a precursor having a labded phen type or a rubbed phen / monazite mixed crystal structure.

  This method is characterized by including the following steps.

  A first solution containing rare earth metal (Ln) chloride is continuously introduced into a second solution containing phosphate ions and having an initial pH of less than 2.

  -During the introduction of the first solution into the second solution, the pH of the resulting medium is controlled at a constant value of less than 2, which results in a precipitate, which for the first stage Setting at a pH of less than or controlling this pH for the second stage, or both, is done at least in part with lithium hydroxide.

  -The resulting precipitate is recovered and optionally calcined at a temperature below 600 ° C.

  The product obtained is again dispersed in hot water and then separated from the liquid medium.

  The various stages of this method will now be described in detail.

  According to the present invention, one or more rare earth metals (Ln) in which a direct precipitation of the rare earth metal (Ln) phosphate at a controlled pH is present in the proportions required to obtain a product of the desired composition. This is performed by reacting the first solution containing the chloride with the second solution containing phosphate ions.

  According to the first important feature of this method, the introduction of the exact sequence of these reactants should be faithfully followed. More specifically, the rare earth metal chloride solution should be introduced gradually and continuously into the solution containing phosphate ions.

  According to a second important feature of this method according to the invention, the initial pH of the solution containing phosphate ions should be less than 2, preferably 1 to 2.

  According to a third feature, the pH of the precipitation medium should then be controlled at a pH value of less than 2, preferably 1 to 2.

  The term “controlled pH” refers to a specific, constant or substantially constant value by the addition of a basic compound to the latter simultaneously with the introduction of a solution containing rare earth metal chloride into a solution containing phosphate ions. This means control of the pH of the precipitation medium. Therefore, the pH of the medium will fluctuate by a maximum of 0.5 pH units before and after the constant value, in particular by a maximum of 0.1 pH before and after this value. The constant value will advantageously correspond to the initial pH (less than 2) of the solution containing phosphate ions.

  The precipitation is preferably carried out in an aqueous medium that is not critical and advantageously at a temperature between room temperature (15 ° C. and 25 ° C.) to 100 ° C. This precipitation is carried out while stirring the reaction medium.

  The concentration of the rare earth metal chloride in the first solution can vary within a wide range. Therefore, the total concentration of rare earth metals may be from 0.01 mol / liter to 3 mol / liter.

  Finally, the rare earth metal chloride solution may also contain other metal salts, in particular chlorides, such as the above mentioned promoter or stabilizer elements, ie boron and other rare earth metal salts. Please keep in mind.

  Phosphate ions intended to react with solutions of rare earth metal chlorides give pure compounds or compounds in solution, eg, phosphates, alkali metal phosphates, or soluble compounds with anions associated with rare earth metals It can be provided by phosphates of other metal elements.

Phosphate ions are present in an amount such that the PO ₄ / Ln molar ratio is greater than 1, preferably 1.1 to 3, between the two solutions.

  As emphasized in the above description, the solution containing phosphate ions is initially a lotus having a pH of less than 2, preferably 1 to 2 (ie before starting the introduction of the rare earth metal chloride solution). Therefore, if the solution used does not inherently have such a pH, by adding a basic compound or by adding an acid (eg hydrochloric acid in the case of an initial solution whose pH is too high) Let the latter be the desired appropriate value.

  Subsequently, during the introduction of the solution containing the rare earth metal chloride, the pH of the precipitation medium gradually decreases, so that according to one of the basic features of the process according to the invention less than 2, preferably 1 to 2 In order to maintain the pH of the precipitation medium at the desired constant working value to be obtained, a basic compound is simultaneously introduced into this medium.

  According to another feature of the method of the invention, the basic compound used to bring the initial pH of the second solution containing phosphate ions to a value less than 2 or to control the pH during precipitation. Is at least partially lithium hydroxide. The term “at least partly” means that it is possible to use a mixture of basic compounds, at least one of which is lithium hydroxide. The other basic compound may be, for example, aqueous ammonia. According to one preferred embodiment, a basic compound that is only lithium hydroxide is used, and according to another even more preferred embodiment, the pH of the second solution is adequate for both of the above operations. Only lithium hydroxide is used in order to obtain a stable value and to control the pH of the precipitate. In these two preferred embodiments, the release of nitrogen products that can be introduced by basic compounds such as aqueous ammonia is reduced or eliminated.

  At the end of the precipitation stage, a rare earth metal (Ln) phosphate is obtained directly, optionally with other elements added. The total concentration of rare earth metals in the final precipitation medium is then advantageously greater than 0.25 mol / liter.

  At the end of the precipitation, aging may be carried out by holding the reaction medium obtained in advance at a temperature within the same temperature range as the temperature at which the precipitation was carried out, and for a period of time, for example 15 minutes to 1 hour. Is possible.

  The phosphate precipitate can be recovered by any means known per se, in particular by simple filtration. This is because, under the conditions of the process according to the invention, a rare earth metal phosphate that is not gelatinous and can be easily filtered out precipitates.

  The recovered product is then washed, for example with water and then dried.

  This product can then be subjected to heat treatment or calcination. The temperature and duration of this calcination will depend on the crystal structure desired for the resulting phosphate. In general, a calcination temperature up to about 400 ° C. makes it possible to obtain a product having a labdofene structure, which is also the structure exhibited by the uncalcined product produced by precipitation. For the rubded phen / monazite mixed type, the calcination temperature is usually at least about 400 ° C., but can extend to a temperature range below 600 ° C., and thus may be 400 ° C. to 500 ° C.

  As an example, this time may be 1 to 3 hours.

  This heat treatment is generally performed in air.

  The higher the calcination temperature, the larger the crystallite size of the phosphate.

  According to another important feature of the invention, the product resulting from calcination, or the product resulting from precipitation in the absence of heat treatment, is then redispersed in hot water.

  This redispersion is carried out by introducing the solid product into water with stirring. The resulting suspension is kept stirred for some time which may be about 1 to 6 hours, especially about 1 to 3 hours.

  The temperature of this water may be at least 30 ° C., in particular at least 60 ° C., and may be about 30 ° C. to 90 ° C., preferably 60 ° C. to 90 ° C. under atmospheric pressure. It is possible to carry out this operation under pressure, for example in an autoclave, which may be from 100 ° C. to 200 ° C., in particular from 100 ° C. to 150 ° C.

  In the last step, the solid is separated from the liquid medium by any means known per se, for example by simple filtration. The redispersion step can optionally be repeated one or more times at a temperature different from the temperature at which the first redispersion was performed, under the conditions described above.

  The separated product can be washed in particular with water and dried.

  In this way, the rare earth metal (Ln) phosphates having the required lithium content and having the labded fen or rubbed phen / monazite structure of the present invention are obtained.

  The method of producing a rare earth metal (Ln) phosphate according to the second embodiment of the present invention, that is, having a monazite-type crystal structure is very close to the method described so far. This method differs from the previous method only because of the fact that the product resulting from precipitation is calcined at a temperature of at least 600 ° C. Accordingly, what has been described above for the previous steps in the method of making the phosphate of the first embodiment applies here as well for the method of making the phosphate of the second embodiment.

  The heat treatment or calcination can be performed in particular at a temperature of 800 to 900 ° C.

  Here again, the higher the calcination temperature, the larger the crystallite size of the phosphate.

  The rest of the process, in particular the step of redispersing in water, is the same as described above for the phosphate according to the first embodiment.

Method of making a phosphor The phosphor of the present invention comprises a phosphate or precursor according to two embodiments as described above, or a phosphate or precursor also obtained by the method described above, at least 1000 ° C. Obtained by calcining at a temperature of This temperature may be about 1000 ° C. to 1300 ° C.

  This treatment converts the phosphate or precursor into a highly efficient phosphor.

This calcination can be carried out in air or in an inert gas, but preferably even in a reducing atmosphere (eg H ₂ , N ₂ / H ₂ or Ar / H ₂ ), and in the last case Ce and Tb. Can be converted to these oxidation states (+ III).

  In known manner, fluxes or solvents such as lithium fluoride, lithium tetraborate, lithium chloride, lithium carbonate, lithium phosphate, potassium chloride, ammonium chloride, boron oxide and boric acid, and ammonium phosphate, and these Calcination can be carried out in the presence of the mixture.

  In the case of using a flux, a phosphor having emission characteristics at least equivalent to those of generally known phosphors can be obtained. The most important advantage of the present invention here is that the phosphors are produced from precursors which themselves are produced by methods which release less nitrogen product than known methods or which do not release any nitrogen product.

  Since calcination can be performed without any flux, it is possible to contribute to reducing the concentration of impurities present in the phosphor without pre-mixing the solvent with the phosphate. is there. In addition, the use of products which, in the case of many of the above-mentioned solvents, may contain nitrogen or must be used within strict safety standards given the toxicity of these possibilities. Is avoided in this way.

  Furthermore, in the case of calcination without flux, it is noted that the precursor of the present invention makes it possible to obtain a phosphor whose emission characteristics are at least equivalent to those of the phosphors obtained from the prior art precursors. I want to be.

  After treatment, the particles are advantageously washed so as to obtain a phosphor that is as pure as possible in a non-agglomerated or low-agglomerated state. In the latter case, the phosphor can be made non-aggregated by subjecting the phosphor to a non-aggregation treatment under mild conditions.

  The phosphor of the present invention has strong emission characteristics against electromagnetic excitation corresponding to various absorption fields of the product.

  Thus, the cerium and terbium based phosphors of the present invention can be used in illumination or display systems having an excitation source in the ultraviolet region (200 to 280 nm), eg around 254 nm. In particular, mention is made of a mercury vapor three-color lamp, a tubular or flat type liquid crystal system backlight lamp (LCD backlight). These lamps have high brightness under ultraviolet excitation, and there is no emission loss due to thermal post-treatment. The light emission of these lamps is particularly stable under relatively high temperature (100 to 300 ° C.) ultraviolet light.

  Phosphors based on terbium and lanthanum according to the invention or based on lanthanum, cerium and terbium are also suitable for example as VUV (or “ Plasma ") is also an excellent candidate as a green phosphor for excitation systems. The emission of the phosphor of the present invention is intense green under VUV excitation (eg, around 147 nm and 172 nm). The phosphor is stable under VUV excitation.

  The phosphor of the present invention can also be used as a green phosphor in a light emitting diode excitation device. These phosphors can be used in particular in systems that can be excited in the near ultraviolet.

  These phosphors can also be used in UV excited marking systems.

  The phosphors of the present invention can also be used in lamp and screen systems by well-known techniques, for example by screen printing, spraying, electrophoresis or sedimentation.

  These phosphors can also be dispersed in organic substrates (such as plastic substrates or polymeric substrates that are transparent under UV light), mineral substrates (such as silica substrates), or mixed organic-mineral substrates.

  According to another aspect, the present invention also relates to a light-emitting device of the type described above, which light-emitting device uses a phosphor as described above or a phosphor also obtained using the method described above as a green light-emitting source. Prepare.

  An example is given here.

  In these examples, as described above, the lithium content is determined by two measurement techniques. In the X-ray fluorescence technique, semi-quantitative analysis is performed on the product powder as it is. The instrument used is a MagiX PRO PW 2540 X-ray fluorescence spectrometer manufactured by PANalytical. The ICP-AES (or OES) technology is implemented by performing quantitative analysis by quantitative addition using an Ultimate instrument made by Jobin Yvon. The sample is previously mineralized (or digested) in a microwave assisted nitric acid-perchloric acid medium in a closed reactor (MARS system-CEM).

  The emission efficiency is determined by comparing the area under the emission spectrum curve from 380 nm to 750 nm recorded using a fluorescence spectrophotometer under excitation at 254 nm and assigning a value of 100% to the area obtained for the comparative product. Measure for powdered product.

(Comparative Example 1)
This example relates to the preparation of lanthanum, cerium and terbium phosphates according to the prior art.

A solution of 4N pure rare earth metal nitrate was added to 1 l of a solution containing 1.73 mol / l of analytical phosphoric acid H ₃ PO ₄ at a pH of 1.6 in advance by addition of aqueous ammonia and 60 ° C. for 1 hour. Add in. The total concentration of the rare earth metal nitrate is 1.5 mol / l, and can be classified as lanthanum nitrate 0.66 mol / l, cerium nitrate 0.65 mol / l, and terbium nitrate 0.20 mol / l as follows. The pH during precipitation is adjusted to 1.6 by adding aqueous ammonia.

At the end of the precipitation stage, the mixture is maintained at 60 ° C. for an additional hour. The resulting precipitate is then collected by filtration, washed with water, then dried in air at 60 ° C. and then heat treated at 840 ° C. in air for 2 hours. At the end of this stage, a precursor having the composition (La _0.44 Ce _0.43 Tb _0.13 ) PO ₄ is obtained.

(Example 2)
This example relates to the preparation of lanthanum, cerium and terbium phosphates according to the present invention.

A solution of 4N purity rare earth metal chloride was added to 1 l of a solution containing 1.5 mol / l of analytical phosphoric acid H ₃ PO ₄ that had previously been brought to pH 1.6 by addition of LiOH and 60 ° C. for 1 hour. Add in. The total concentration of rare earth metal chlorides is 1.3 mol / l, and can be classified as follows: lanthanum chloride 0.57 mol / l, cerium chloride 0.56 mol / l, terbium chloride 0.17 mol / l. The pH during precipitation is adjusted to 1.6 by the addition of LiOH.

At the end of the precipitation stage, the mixture is maintained at 60 ° C. for a further 15 minutes. The resulting precipitate is then collected by filtration, washed with water, then dried in air at 60 ° C. and then heat treated at 840 ° C. in air for 2 hours. At the end of this calcination, the product obtained is redispersed in 80 ° C. water for 3 hours, then washed and filtered and finally dried. At the end of this stage, a precursor having the composition (La _0.44 Ce _0.43 Tb _0.13 ) PO ₄ is obtained.

  The properties of the products of Examples 1 and 2 are shown in Table 1 below.

  The precursor phosphate of the present invention is more crystallized than the precursor phosphates of the prior art, while at the same time retaining similar particle size characteristics.

(Comparative Example 3)
This example relates to the preparation of a phosphor from the phosphate of Example 1 according to the prior art.

The precursor phosphate obtained in Example 1 is reprocessed at 1000 ° C. for 2 hours under a reducing atmosphere (Ar / H ₂ ). The resulting calcined product is then washed in warm water at 80 ° C. for 3 hours, then filtered and dried.

Example 4
This example relates to the preparation of a phosphor according to the invention obtained from the phosphate salt of example 2.

  The precursor phosphate obtained in Example 2 is reprocessed under the same conditions as in Example 3.

  The properties of the products of Examples 3 and 4 are shown in Table 2 below.

  The luminous efficiency of the product 4 according to the invention is given for the comparative product 3.

Claims (22)

Rare earth metal phosphate in which the rare earth metal (Ln) represents at least one rare earth metal selected from cerium and terbium, or lanthanum in combination with at least one of the above two rare earth metals, and is of orthophosphate type And having a rubudophene or rubdofen / monazite mixed crystal structure, containing lithium, having a lithium content of up to 300 ppm, and the phosphate having an average diameter of 1 μm to 15 μm, Rare earth metal phosphate characterized in that the particles are particles having a dispersion index of up to 0.5 .   2. Phosphate according to claim 1, characterized in that it consists of crystallites whose size measured in the (012) plane is at least 25 nm. Rare earth metal phosphate in which the rare earth metal (Ln) represents at least one rare earth metal selected from cerium and terbium, or lanthanum in combination with at least one of the above two rare earth metals, and is of orthophosphate type Having a monazite-type crystal structure, containing lithium, having a lithium content of up to 300 ppm, and having a mean diameter of 1 μm to 15 μm and a dispersion of up to 0.5 A rare earth metal phosphate characterized by being a particle having an index .   4. Phosphate according to any one of claims 1 to 3, characterized in that the lithium content is at least 10 ppm.   4. Phosphate according to any one of claims 1 to 3, characterized in that the lithium content is at least 90 ppm.   The phosphate according to any one of claims 3 to 5, characterized in that it consists of crystallites having a size measured in the (012) plane of at least 70 nm. Characterized in that the phosphate has not been calcined or has been calcined at a temperature not exceeding 900 ° C. and is redispersed in warm water and separated from the liquid in the last step. The phosphate according to any one of claims 1 to 6. The phosphate according to claim 1, wherein the phosphate is a particle having an average diameter of 2 μm to 6 μm. 9. Phosphate according to any one of claims 1 to 8, characterized in that the phosphate is a particle having a dispersion index of at most 0.4. A product having the following general formula (I):
_{La x Ce y Tb z PO 4} (1)
The phosphate according to claim 1, wherein the sum of x + y + z is equal to 1 and at least one of y and z is other than 0. 11. Phosphate according to claim 10, characterized in that x is between 0.4 and 0.95. Rare earth metal phosphate in which the rare earth metal (Ln) represents at least one rare earth metal selected from cerium and terbium, or lanthanum in combination with at least one of the above two rare earth metals, and is of orthophosphate type Based phosphors, having a monazite-type crystal structure, containing lithium, having a maximum lithium content of 75 ppm, the phosphate having an average diameter of 1 μm to 15 μm and a maximum of 0 A phosphor having a dispersion index of .5 . The phosphor according to claim 12 , characterized in that it consists of particles with a coherent length measured at the (012) plane of at least 300 nm. The phosphor according to claim 12 or 13 , characterized in that the lithium content is at least 10 ppm. 15. A phosphor according to any one of claims 12 to 14, characterized in that the phosphor is in a non-aggregated state. The phosphor according to any one of claims 12 to 15, wherein the phosphate is a particle having an average diameter of 2 µm to 6 µm. 17. A phosphor according to any one of claims 12 to 16, characterized in that the phosphate is a particle having a dispersion index of at most 0.4. A method for producing a rare earth metal phosphate according to any one of claims 1, 2, and 4 to 11 , comprising:
-A first stage of continuously introducing a first solution containing rare earth metal (Ln) chloride into a second solution containing phosphate ions and having an initial pH of less than 2;
-During the introduction of the first solution into the second solution, the second stage in which the pH of the resulting medium is controlled to a constant value of less than 2, whereby a precipitate is obtained, the first stage Oite second solution to set at less than 2 pH, or controlling the Oite pH in the second stage, or both are at least partially carried out using lithium hydroxide,
-Collecting the resulting precipitate and optionally calcining at a temperature below 600 ° C;
-The method comprising the step of re-dispersing the product obtained in warm water and then separating it from the liquid medium. A method for producing a rare earth metal phosphate according to any one of claims 3 to 11 , comprising:
-A first stage of continuously introducing a first solution containing rare earth metal (Ln) chloride into a second solution containing phosphate ions and having an initial pH of less than 2;
-During the introduction of the first solution into the second solution, the second stage in which the pH of the resulting medium is controlled to a constant value of less than 2, whereby a precipitate is obtained, the first stage Oite second solution to set at less than 2 pH, or controlling the Oite pH in the second stage, or both are at least partially carried out using lithium hydroxide,
-Collecting the resulting precipitate and calcining at a temperature of at least 600 ° C;
-The method comprising the step of re-dispersing the product obtained in warm water and then separating it from the liquid medium. That rare earth metal phosphate obtained by the method according to the rare earth metal phosphate or claim 18 or 19 according to any one of claims 1 to 11 is calcined at a temperature of at least 1000 ° C. 18. A method of making a phosphor according to any one of claims 12 to 17 , characterized in that 21. A method according to claim 20 , characterized in that the calcination is carried out under a reducing atmosphere. 18. A plasma system, a mercury vapor lamp, a backlight lamp for a liquid crystal system, a three-color lamp without mercury, a device for excitation by light-emitting diodes or a device of the ultraviolet excitation marking system type. A device comprising or using a phosphor according to claim 20 or a phosphor obtained by the method according to claim 20 or 21 .